CN115397898A - Epoxy resin composition for fiber-reinforced composite material, prepreg, and fiber-reinforced composite material - Google Patents

Epoxy resin composition for fiber-reinforced composite material, prepreg, and fiber-reinforced composite material Download PDF

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Publication number
CN115397898A
CN115397898A CN202080099865.1A CN202080099865A CN115397898A CN 115397898 A CN115397898 A CN 115397898A CN 202080099865 A CN202080099865 A CN 202080099865A CN 115397898 A CN115397898 A CN 115397898A
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epoxy resin
fiber
resin composition
reinforced composite
composite material
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CN115397898B (en
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上村幸弘
伊藤友裕
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Yokohama Rubber Co Ltd
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Yokohama Rubber Co Ltd
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
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    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
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    • C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
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    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
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Abstract

An epoxy resin composition for fiber-reinforced composite materials, which can be molded at low temperatures and low pressures, has practically sufficient heat resistance and mechanical properties, and can be produced at a significantly reduced production cost, is obtained by compounding (a) 1 or 2 or more epoxy resins, (b) an aromatic diamine compound, (c) dicyandiamide, (d) a urea compound, and (e) an amine adduct compound in a specific range.

Description

Epoxy resin composition for fiber-reinforced composite material, prepreg, and fiber-reinforced composite material
Technical Field
The present invention relates to an epoxy resin composition for a fiber-reinforced composite material, a prepreg, and a fiber-reinforced composite material.
Background
Epoxy resins have been the mainstream of matrix resins for carbon fiber and glass fiber reinforced composite materials (FRPs) used in aircraft and the like, and have been used in many airframe structures. For example, patent document 1 discloses an epoxy resin composition containing an epoxy resin as a matrix, a thermoplastic resin for adjusting viscosity, a filler, and a curing agent, and also discloses a prepreg obtained by compounding the composition with reinforcing fibers.
The heat resistance requirements in an aircraft are determined by location, for example roughly divided into about 95 ℃ (above) and about 70 ℃. Compounding of epoxy resin compositions to meet these requirements can be classified into 180 ℃ curing type compounding and 120 ℃ curing type compounding, and 180 ℃ cured products and 120 ℃ cured products can be obtained depending on the respective curing temperatures.
On the other hand, FRP is indicated to take a manufacturing cost. In particular, in the step of curing and molding a prepreg by an autoclave through a mechanical or manual method, a large amount of auxiliary material cost used for bagging before curing, and autoclave facility management cost and energy cost are large, and are considered to be main factors for increasing the production cost. Therefore, research and development have been actively conducted on a method for producing FRP without using prepreg or autoclave, such as Filament Winding (FW) and Resin Transfer (RTM) molding. However, from the viewpoint of quality reproducibility and reliability of the produced parts, it is not possible to obtain a level equal to or higher than that of the above-described hand lay-up-autoclave molding method of a prepreg. Since the manufacturing cost when an autoclave is used is increased in proportion to the curing temperature, pressure, and time, if a prepreg material that can be cured at a slightly low temperature and a low pressure can be used, the manufacturing cost of the autoclave having the highest reliability can be reduced. For example, if the processes now divided into 120 ℃ curing and 180 ℃ curing can be unified into 120 ℃ curing on the low temperature side, the efficiency of curing by an autoclave can be improved, and the reduction of the manufacturing cost can be greatly facilitated.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2011-99094
Disclosure of Invention
Problems to be solved by the invention
Accordingly, an object of the present invention is to provide an epoxy resin composition for fiber-reinforced composite materials, a prepreg, and a fiber-reinforced composite material, which can be molded at low temperature and low pressure, have practically sufficient heat resistance and mechanical properties, and can be manufactured at a significantly reduced cost.
Means for solving the problems
As a result of intensive studies, the present inventors have found that the above problems can be solved by a resin composition in which (a) 1 or 2 or more kinds of epoxy resins, (b) an aromatic diamine compound, (c) dicyandiamide, (d) a urea compound, and (e) an amine adduct compound are blended in a specific amount, and have completed the present invention.
That is, the present invention provides an epoxy resin composition for a fiber-reinforced composite material, which is obtained by compounding (a) 1 or 2 or more kinds of epoxy resins, (b) an aromatic diamine compound, (c) dicyandiamide, (d) a urea compound, and (e) an amine adduct compound at the following compounding ratio.
The compounding ratio of the aromatic diamine compound (b) is 0.2 to 0.6 equivalent to the epoxy resin (a);
the blending ratio of the dicyandiamide (c) is 0.5 to 4.0 mass% with respect to the whole of the components (a) to (e);
the proportion of the urea compound (d) is 0.5 to 2.0% by mass based on the total of the components (a) to (e); and
the proportion of the amine adduct compound (e) is 0 to 3.0% by mass based on the total of the components (a) to (e).
ADVANTAGEOUS EFFECTS OF INVENTION
The epoxy resin composition for a fiber-reinforced composite material (hereinafter, may be simply referred to as a resin composition) of the present invention is obtained by compounding (a) 1 or 2 or more kinds of epoxy resins, (b) an aromatic diamine compound, (c) dicyandiamide, (d) a urea compound, and (e) an amine adduct compound in specific amounts, and therefore can be molded at low temperature and low pressure, has practically sufficient heat resistance and mechanical properties, and can significantly reduce the production cost.
In particular, the resin composition of the present invention can be cured at 120 ℃ on the low temperature side by combining the processes of curing at 120 ℃ and curing at 180 ℃. For example, when the prepreg of the present invention is cured under low-temperature and low-pressure conditions (e.g., 120 ℃,90 minutes, 0.31 MPa) in an autoclave, FRP having heat resistance and mechanical properties equivalent to those of the 120 ℃ cured product of the prior art can be obtained. Furthermore, by post-curing the cured product (for example, 180 ℃ C., 2 hours, atmospheric pressure), FRP having heat resistance and mechanical properties equivalent to those of the conventional 180 ℃ cured product can be obtained. The post-curing does not require pressurization using an autoclave, and for example, only heating using an air circulation oven or the like is sufficient. Therefore, in the case of producing a 180 ℃ cured product, an auxiliary material necessary for the 180 ℃ curing by an autoclave is not required, and the production cost in the case of using an autoclave can be reduced. In addition, since the product can be released from the lamination jig and heated in an independent state at the time of post-curing, productivity can be improved by shortening the time taken for the mold. In addition, the prepreg of the present invention can be used to produce a 180 ℃ cured product using an autoclave, and in this case, a cured product having molding quality, heat resistance, and mechanical properties equivalent to those of a conventional 180 ℃ cured product can be obtained.
Further, as described above, according to the present invention, in both the case of producing a 120 ℃ cured product and the case of producing a 180 ℃ cured product, it is only necessary to produce the 120 ℃ cured product first, and therefore, it is not necessary to prepare materials corresponding to the respective cured products as in the prior art, and it is also not necessary to store and manage the respective cured products, and it is possible to reduce the production cost.
As described above, according to the present invention, it is possible to provide an epoxy resin composition for fiber-reinforced composite material, a prepreg, and a fiber-reinforced composite material, which can be molded at low temperature and low pressure, have practically sufficient heat resistance and mechanical properties, and can significantly reduce the production cost.
Detailed Description
The present invention will be described in further detail below.
The resin composition of the present invention is characterized by being obtained by compounding (a) 1 or 2 or more epoxy resins, (b) an aromatic diamine compound, (c) dicyandiamide, (d) a urea compound, and (e) an amine adduct compound at the following compounding ratio.
The compounding ratio of the aromatic diamine compound (b) is 0.2 to 0.6 equivalent relative to the epoxy resin (a);
the blending ratio of the dicyandiamide (c) is 0.5 to 4.0 mass% based on the whole of the components (a) to (e);
the proportion of the urea compound (d) is 0.5 to 2.0% by mass relative to the total of the components (a) to (e); and
the blending ratio of the amine adduct compound (e) is 0 to 3.0% by mass based on the whole of the components (a) to (e).
(a) Epoxy resin
In a suitable embodiment, the epoxy resin (a) may be composed entirely of 3-or more-functional epoxy resins. In addition, the (a) epoxy resin may be a 2-functional epoxy resin in combination, and in this case, the (a) epoxy resin is preferably composed of 0 to 80% by mass of the 2-functional epoxy resin and 20 to 100% by mass of the 3-functional or higher epoxy resin.
Examples of the epoxy resin having 3 or more functions include polyfunctional glycidyl ether type epoxy resins such as phenol novolak type, o-cresol novolak type, trishydroxyphenylmethane type, and tetraphenolethane type, and glycidyl amine type epoxy resins such as tetraglycidyl diaminodiphenylmethane, tetraglycidyl-m-xylylenediamine, triglycidyl-p-aminophenol, and triglycidyl-m-aminophenol.
The 3-or higher-functional epoxy resin is preferably a liquid or semisolid epoxy resin from the viewpoint of higher heat resistance, more appropriate viscosity, and excellent workability (for example, impregnation into a fiber base material).
The epoxy resins having 3 or more functions may be used singly or in combination of 2 or more.
Examples of the 2-functional epoxy resin include epoxy compounds having a biphenyl group such as bisphenol a type, bisphenol F type, brominated bisphenol a type, hydrogenated bisphenol a type, bisphenol S type, bisphenol AF type, biphenyl type, polyalkylene glycol type, alkylene glycol type, epoxy compounds having a naphthalene ring, epoxy compounds having a fluorenyl group, and the like.
The 2-functional epoxy resins may be used singly or in combination of 2 or more, respectively.
(b) Aromatic diamine compound
(b) The aromatic diamine compound has an effect of curing the epoxy resin (a). The aromatic diamine compound (b) used in the present invention is not particularly limited as long as it has the above-mentioned action, but preferably 1 or more selected from 3,3 '-diaminodiphenyl sulfone, 4,4' -diaminodiphenyl sulfone, 4,4 '-methylenebis (2,6-diethylaniline) and 4,4' -methylenebis (2-ethyl-6-methyl) aniline, from the viewpoint of improving the effect of the present invention.
The structures of these suitable (b) aromatic diamine compounds are shown below.
Figure BDA0003888243200000051
In the resin composition of the present invention, the blending ratio of the aromatic diamine compound (b) is 0.2 to 0.6 equivalent to the epoxy resin (a). If the amount is outside the range of the compounding ratio, the heat resistance is lowered. (b) The preferred compounding ratio of the aromatic diamine compound is 0.3 to 0.5 equivalent to the epoxy resin (a).
(c) Dicyandiamide
(c) Dicyandiamide has an action of curing the epoxy resin (a), and has the following structure.
Figure BDA0003888243200000061
In the resin composition of the present invention, the blending ratio of the dicyandiamide (c) is 0.5 to 4.0% by mass based on the whole of the components (a) to (e). If the amount is outside this range, the heat resistance is lowered or the curability at a low temperature such as 120 ℃ is lowered. (c) The preferred blending ratio of dicyandiamide is 1.0 to 3.0% by mass of the total of components (a) to (e).
(d) Urea compounds
(d) The urea compound has an action of accelerating the curing reaction of the epoxy resin (a). The urea compound (d) used in the present invention is not particularly limited as long as it has the above-mentioned action, but from the viewpoint of improving the effect of the present invention, it is preferably 1 or more selected from the group consisting of 3- (3,4 '-dichlorophenyl) -1,1-dimethylurea, 2,4-tolylenedidimethylurea and 4,4' -methylenebis (phenyldimethylurea).
The structures of these suitable (d) urea compounds are shown below.
Figure BDA0003888243200000062
In the resin composition of the present invention, the blending ratio of the urea compound (d) is 0.5 to 2.0% by mass based on the whole of the components (a) to (e). If the amount is outside this range, the heat resistance and curability are reduced. (d) The preferred mixing ratio of the urea compound is 0.5 to 1.5% by mass based on the whole of the components (a) to (e).
(e) Amine adduct compounds
(e) The amine adduct compound has an action of accelerating the curing reaction of the (a) epoxy resin. (e) The amine adduct compound is an adduct of an amine, and for example, an adduct of an amine and at least 1 compound selected from the group consisting of an epoxy resin, an isocyanate compound and a urea compound is exemplified.
The amine may be, for example, one having 1 or more active hydrogens capable of undergoing an addition reaction with an epoxy group, a phenol group, or an isocyanate group in 1 molecule, and having 1 or more at least 1 selected from primary, secondary, and tertiary amino groups in 1 molecule. Specific examples thereof include 2-methylimidazole, N-methylimidazole, 2-ethyl-4-methylimidazole, N-methylpiperazine, 2,4,6-tris (dimethylaminomethyl) phenol, 2-dimethylaminoethanol (2- ジマチルアミノエタノール), 2-undecylimidazole, 2-phenylimidazole and 2-octadecylimidazole.
The epoxy resin is not particularly limited. Examples thereof include polyglycidyl ethers obtained by reacting epichlorohydrin with polyhydric phenols such as bisphenol a, bisphenol F, bisphenol AD, catechol, and resorcinol, and polyhydric alcohols such as glycerin and polyethylene glycol; glycidyl ether esters obtained by reacting a hydroxycarboxylic acid such as p-hydroxybenzoic acid or β -hydroxynaphthoic acid with epichlorohydrin; polyglycidyl esters obtained by reacting epichlorohydrin with polycarboxylic acids such as phthalic acid and terephthalic acid; glycidyl amine type epoxy resins obtained from epoxidized phenol novolak resins, epoxidized cresol novolak resins, epoxidized polyolefins, cyclic aliphatic epoxy resins, urethane-modified epoxy resins, 4,4 diaminodiphenylmethane, m-aminophenol, and the like.
The isocyanate compound is not particularly limited. Examples thereof include monofunctional isocyanate compounds such as n-butyl isocyanate, phenyl isocyanate and 1,6-hexamethylene diisocyanate; 1,6-hexamethylene diisocyanate, toluene diisocyanate, 1,5-naphthalene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, 1,3,6-hexamethylene triisocyanate, and the like.
The urea compound is not particularly limited as long as it is a compound having at least 1 selected from the group consisting of a urea group linkage, a ureylene group linkage, and NH-CO-N. Examples thereof include urea, urea phosphate, urea oxalate, urea acetate, diacetyl urea, dibenzoyl urea, and trimethyl urea.
In the resin composition of the present invention, the blending ratio of the amine adduct compound (e) is 0 to 3.0% by mass based on the whole of the components (a) to (e). When the compounding ratio of the (e) amine adduct compound exceeds 3.0 mass%, the balance in the curability of the resin is lost, the low-temperature curability at 120 ℃ is deteriorated, and the heat resistance of the cured product is lowered. (e) The preferable blending ratio of the amine adduct compound is 0 to 2% by mass with respect to the whole of the components (a) to (e).
In the resin composition of the present invention, additives corresponding to the purpose of use may be added within a range not departing from the object of the present invention. Examples of the component that can be added include flame retardants, thermoplastic resins for improving toughness of a cured resin, rubbers, resin fluidity control during curing, and inorganic particles for improving rigidity of a resin.
The resin composition of the present invention has excellent curability. For example, the composition can be cured under curing conditions of 120 ℃ for 1.5 hours to a state in which the composition can be released from a mold. The obtained cured product has a glass transition temperature of 110 ℃ or higher and high heat resistance. Since the reaction initiation temperature (exothermic peak initiation temperature) obtained by differential scanning calorimetry (DSC analysis) with a temperature rise rate of 10 ℃/min is 90 ℃ or more and 120 ℃ or less, the resin composition of the present invention can be cured reliably at 120 ℃.
The glass transition temperature in the present invention is measured by thermomechanical analysis (TMA), and specific conditions are as follows.
The use equipment comprises the following steps: model TMA4000S thermomechanical analyzer manufactured by ブルカー, エイエックスエス
Temperature rise rate: 10 deg.C/min
Measurement mode: expansion mode
Applying a load: 2g
And (3) measuring the atmosphere: air (a)
The specific conditions for the DSC analysis are as follows.
The use equipment comprises the following steps: DSC2500 type differential scanning calorimeter of TA インスツルメント
Temperature rise rate: 10 ℃/min
And (3) measuring the atmosphere: nitrogen gas
In the present invention, the cured product is post-cured (for example, at 180 ℃ C. For 2 hours under atmospheric pressure), whereby a cured product having heat resistance and mechanical properties equivalent to those of a conventional 180 ℃ cured product can be obtained. The post-curing does not require pressurization using an autoclave, and for example, only heating using an air circulation oven or the like is sufficient. Therefore, an auxiliary material necessary for curing at 180 ℃ by using an autoclave is not required, and the manufacturing cost in the case of using an autoclave can be reduced. In addition, since the product can be released from the lamination jig and heated in an independent state at the time of post-curing, productivity can be improved by shortening the mold occupation time.
The glass transition temperature of the post-cured product is 180 ℃ or higher, and the post-cured product has high heat resistance.
The prepreg of the present invention is obtained using the resin composition of the present invention and a fibrous base material.
Specifically, the prepreg of the present invention is obtained by impregnating a fibrous base material with the resin composition of the present invention.
The fiber base material used in the prepreg of the present invention is not particularly limited, and is preferably any of, for example, glass fiber, quartz fiber, aramid fiber, and carbon fiber. Examples of the form of the fiber base material include woven fabric, roving, nonwoven fabric, knitted fabric, and tissue.
The method for producing the prepreg of the present invention is not particularly limited. Examples thereof include an immersion method using a solvent and a hot melt method which is a solvent-free method.
The fiber-reinforced composite material of the present invention is a cured product of the prepreg of the present invention. The use of the fiber-reinforced composite material of the present invention is not particularly limited, and examples thereof include aircraft parts such as antenna covers, cowlings, flaps, leading edges, floors, propellers, and fuselages; motorcycle parts such as motorcycle frames, cowl panels, fenders, etc.; automobile parts such as a door, a hood, a tailgate, a side fender, a side panel, a fender, an energy absorbing member, a trunk lid, a hard roof, an outer rear mirror cover, a spoiler, a diffuser, a snowboard mounting frame, an engine cylinder head, an engine hood, a chassis, an air spoiler, a transmission shaft, and the like; outer panels for vehicles such as a head car, a roof, side panels, doors, a hood, and side skirts; parts of railway vehicles such as luggage racks and seats; interior trims, inner panels, outer panels, roofs, floors, and the like of wings in wing cars, and streamlined parts such as side skirts attached to automobiles and bicycles; the use of casings for notebook personal computers, cellular phones, and the like; medical uses such as X-ray cassettes and top plates; acoustic products such as flat speaker panels and speaker cones; sports goods such as golf club heads, diving masks, snowboards, surfboards, and protectors; leaf springs, wind turbine blades, elevators (box panels, doors), and the like.
Examples
The present invention will be further illustrated by the following examples and comparative examples, but the present invention is not limited to the following examples.
Examples 1 to 4 and comparative examples 1 to 8
In examples and comparative examples, the following materials were used.
(a) Epoxy resin
An epoxy resin having 3 or more functional groups (iron-I ケミカル & マテリアル (available from ed.) YH-404 with an epoxy equivalent = 115)
An epoxy resin having 3 or more functions (MY-0510 manufactured by Huntsman Advanced materials, epoxy equivalent = 101)
Epoxy resin having 3 or more functions ((VG 3101L made by プリンテック, epoxy equivalent =210, ltd.))
2-functional epoxy resin (YD-128 manufactured by Nizhi ケミカル & マテリアル K.K., epoxy equivalent = 191)
2-functional epoxy resin (HP-4032 SS manufactured by DIC Ltd., epoxy equivalent = 143). 2-functional epoxy resin (Epox MKSR35K manufactured by プリンテック, epoxy equivalent = 962)
(b) Aromatic diamine
4,4' -diaminodiphenyl sulfone (manufactured by Harris mountain industries Co., ltd.)
(c) Dicyandiamide
Dicyandiamide (Dicy 15 manufactured by Mitsubishi ケミカル, ltd.)
(d) Urea compounds
4,4' -methylenebis (phenyldimethylurea) (CVC Thermoset Specialities, omicure U-24M)
(e) Amine adduct compounds
An amine-epoxy adduct compound (Nazisu ファインテクノ, manufactured by PN-40J)
The respective materials were kneaded using a kneader at compounding ratios (parts by mass) shown in table 1 below to prepare resin compositions.
Next, the prepared resin composition was injected into a mold having dimensions of 200mm X3 mm, and then heated at 120 ℃ for 1.5 hours, thereby attempting to produce a cured product at 120 ℃. Table 1 shows the curability, the appearance of the resulting cured product, and the glass transition temperature. The glass transition temperature was measured by cutting a part of the cured resin into a square of about 3 mm.
Then, the 120 ℃ cured product, 180 ℃,3 hours post curing, manufacturing 180 ℃ cured product. The post-curing is carried out by heating the cured resin in an air circulation oven under atmospheric pressure in a state independent of the use of a mold. The appearance and glass transition temperature of the resulting cured product were examined.
The results are shown in table 1, respectively.
The following mechanical properties were measured for the 120 ℃ cured product and the 180 ℃ cured product obtained above.
Tensile Strength (measured according to ASTM D638)
Tensile modulus of elasticity (measured according to ASTM D638)
Tensile elongation (measured according to ASTM D638)
Flexural Strength (measured according to ASTM D790)
Flexural modulus of elasticity (measured according to ASTM D790)
Flexural elongation (measured according to ASTM D790)
Tensile toughness (calculated from load-strain curve in tensile test)
Bending toughness (calculated from load-strain curve in bending test)
The results are shown in table 2.
Figure BDA0003888243200000121
Figure BDA0003888243200000131
From the results of tables 1 and 2, it was confirmed that: in each example, the curing was performed well at 120 ℃ and the heat resistance and mechanical properties of the obtained cured product were also practically sufficient. Further, it was confirmed that a 180 ℃ cured product obtained by post-curing a 120 ℃ cured product at 180 ℃ was also practically sufficient in heat resistance and mechanical properties.
In contrast, in comparative examples 1 and 2, the dicyandiamide (c) and the urea compound (d) of the present invention were not mixed, and the curing at 180 ℃ was confirmed, but the curing was not possible at 120 ℃.
In comparative example 3, the compounding ratio of the component (c) exceeds the upper limit defined in the present invention, and therefore, the heat resistance of the cured product at 180 ℃ is deteriorated.
In addition, comparative examples 4 to 8 were only subjected to confirmation of the degree of curing, and the results are shown in table 1.

Claims (13)

1. An epoxy resin composition for fiber-reinforced composite materials, characterized in that it is obtained by compounding (a) 1 or 2 or more epoxy resins, (b) an aromatic diamine compound, (c) dicyandiamide, (d) a urea compound, and (e) an amine adduct compound at the following compounding ratio,
the compounding ratio of the aromatic diamine compound (b) is 0.2 to 0.6 equivalent relative to the epoxy resin (a);
the blending ratio of the dicyandiamide (c) is 0.5 to 4.0 mass% with respect to the whole of the components (a) to (e);
the proportion of the urea compound (d) is 0.5 to 2.0% by mass relative to the total of the components (a) to (e); and is provided with
The blending ratio of the amine adduct compound (e) is 0 to 3.0% by mass relative to the whole of the components (a) to (e).
2. The epoxy resin composition for fiber-reinforced composite material according to claim 1, which is cured under curing conditions of 120 ℃ and 1.5 hours until the state in which the epoxy resin composition can be released from a mold, and the glass transition temperature of the obtained cured product is 110 ℃ or higher.
3. The epoxy resin composition for fiber-reinforced composite material according to claim 2, wherein the cured product has a glass transition temperature of 180 ℃ or higher by post-curing at 180 ℃ for 2 hours.
4. The epoxy resin composition for fiber-reinforced composite material according to claim 1, wherein the epoxy resin (a) comprises 0 to 80% by mass of a 2-functional epoxy resin and 20 to 100% by mass of a 3-functional or higher epoxy resin.
5. The epoxy resin composition for fiber-reinforced composite material according to claim 1, wherein an exothermic peak start temperature, which is a reaction start temperature obtained by DSC analysis, which is a differential scanning calorimetry analysis with a temperature rise rate of 10 ℃/min, is 90 ℃ or higher and 120 ℃ or lower.
6. The epoxy resin composition for fiber-reinforced composites according to claim 1, wherein the (b) aromatic diamine compound is 1 or more selected from 3,3 '-diaminodiphenyl sulfone, 4,4' -diaminodiphenyl sulfone, 4,4 '-methylenebis (2,6-diethylaniline) and 4,4' -methylenebis (2-ethyl-6-methyl) aniline.
7. The epoxy resin composition for fiber-reinforced composite material according to claim 1, wherein the urea compound (d) is 1 or more selected from the group consisting of 3- (3,4 '-dichlorophenyl) -1,1-dimethylurea, 2,4-tolylenedidimethylurea and 4,4' -methylenebis (phenyldimethylurea).
8. The epoxy resin composition for fiber-reinforced composite material according to claim 1, wherein the blending ratio of the aromatic diamine compound (b) is 0.3 to 0.5 equivalent to the epoxy resin (a).
9. The epoxy resin composition for fiber-reinforced composite material according to claim 1, wherein the blending ratio of the dicyandiamide (c) is 1.0 to 3.0% by mass based on the whole of the components (a) to (e).
10. The epoxy resin composition for fiber-reinforced composite material according to claim 1, wherein the urea compound (d) is contained in an amount of 0.5 to 1.5% by mass based on the total amount of the components (a) to (e).
11. The epoxy resin composition for fiber-reinforced composite material according to claim 1, wherein the blending ratio of the amine adduct compound (e) is 0 to 2% by mass based on the total of the components (a) to (e).
12. A prepreg obtained by impregnating any one of glass fibers, quartz fibers, aramid fibers and carbon fibers with the epoxy resin composition for fiber-reinforced composite materials according to claim 1.
13. A fiber-reinforced composite material which is a cured product of the prepreg according to claim 12.
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